JP6325887B2 - LAMINATE FOR PATTERN FORMATION, METHOD FOR MANUFACTURING PATTERN WITH PATTERN, AND PATTERN WITH PATTERN - Google Patents

Description

  The present invention relates to a laminate for pattern formation, a method for producing a substrate with a pattern, and a substrate with a pattern.

  As a general pattern forming method for a resin layer made of a photosensitive resin, photolithography and a direct drawing method are known.

  In photolithography, a photosensitive resin composition layer made of a photosensitive resin composition is formed on a substrate, the photosensitive resin composition layer is cured by exposure of a predetermined pattern, and unexposed portions are removed by development to be predetermined. A cured film of a pattern is formed. For example, Patent Document 1 discloses that a photomask is placed on a laminate having a photosensitive resin layer, and a pattern is formed on the photosensitive resin layer by exposing and developing the photosensitive resin layer. Yes.

  Further, for example, Patent Document 2 discloses that a predetermined portion of the photosensitive resin layer is irradiated with actinic rays to form a photocured portion in the exposure step. Here, as a method for forming the photocured portion, there is a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an artwork.

  By the pattern forming method as described above, the photosensitive resin layer can be patterned into a desired shape such as fine lines, dots, squares, etc., and the method of patterning the photosensitive resin layer more finely or more easily Development is active.

International Publication No. 2012/067107 Pamphlet JP 2012-108235 A

  However, according to the method disclosed in Patent Document 1, an organic solvent or an alkaline aqueous solution harmful to the environment and the human body is used in the step of laminating the photosensitive resin layer to the base material, the exposure step, and the development step. There is a need.

  An object of this invention is to provide the manufacturing method of the laminated body for pattern formation which can form a pattern easily without a image development process, a base material with a pattern, and a base material with a pattern.

The laminate for forming a pattern of the present invention has a resin layer composed of a photosensitive resin material, a first base material bonded to one main surface of the resin layer, and an adhesive main surface to the other main surface of the resin layer. And at least one of the first substrate and the second substrate is made of a resin containing a fluorine compound on at least a part of the surface in contact with the resin layer. When a concavo-convex structure is formed and the resin layer is exposed with a desired pattern to form an unexposed portion and an exposed portion, in the unexposed portion, the adhesion to the first base material is the second It becomes larger than the adhesiveness with the base material, and the adhesiveness with the first base material is smaller than the adhesiveness with the second base material in the exposed portion of the resin layer. Features.

  With this configuration, the resin layer can be easily patterned without a development step by utilizing the difference in adhesion to the first base material and the second base material in the unexposed part and the exposed part of the resin layer. Is possible.

  In the laminated body for pattern formation of the present invention, it is preferable that the concavo-convex structure has a periodic arrangement.

  The laminate for pattern formation of the present invention is characterized in that a material different from the photosensitive resin material is present in at least a part of the concave portion of the concavo-convex structure.

  In the laminate for forming a pattern according to the present invention, it is preferable that at least one of the first base material and the second base material is at least partially composed of an inorganic material.

  In the laminated body for pattern formation of the present invention, the inorganic material is preferably a metal material including a metal, a metal oxide, a metal nitride, or a semiconductor material.

  In the laminate for pattern formation of the present invention, the metal oxide is at least one selected from the group consisting of a transparent conductor, silicon oxide, aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, barium titanate, and strontium titanate. Preferably it is a seed.

  In the laminate for pattern formation of the present invention, the transparent conductor is preferably at least one selected from the group consisting of ITO, IZO, ATO, AZO, GZO, TTO, NTO, tin oxide and zinc oxide.

  In the laminated body for pattern formation of the present invention, it is preferable that the semiconductor material is Si, SiC, Ge, or a III-V group compound.

  In the pattern forming laminate of the present invention, the metal is preferably at least one selected from the group consisting of Al, Mo, Au, Ag, Cu, and Ti.

  The manufacturing method of the base material with a pattern of this invention is the exposure which exposes the said resin layer through the mask which has a desired pattern with respect to said laminated body for pattern formation, and forms the said exposed part and the said unexposed part. And a peeling step of peeling the laminate for pattern formation into the second base material to which the unexposed portion is bonded and the second base material to which the exposed portion is bonded. It is characterized by.

  With this configuration, the resin layer can be easily patterned without a development step by utilizing the difference in adhesion to the first base material and the second base material in the unexposed part and the exposed part of the resin layer. It becomes possible to produce a substrate with a pattern.

  In the manufacturing method of the base material with a pattern of this invention, it is preferable to further include the heating process which heats the said laminated body for pattern formation after the said exposure process.

  The patterned substrate of the present invention is manufactured by the above-described method for manufacturing a patterned substrate.

  According to the present invention, the resin layer can be easily formed without a development step by utilizing the difference in adhesion between the unexposed portion and the exposed portion of the resin layer with respect to each of the first base material and the second base material. A laminate for pattern formation that can be patterned, a method for producing a patterned substrate, and a patterned substrate can be provided.

It is a cross-sectional schematic diagram which shows the laminated body for pattern formation which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows each process of the manufacturing method of the laminated body for pattern formation which concerns on this Embodiment, and the manufacturing method of a base material with a pattern. It is explanatory drawing for demonstrating the uneven structure in the laminated body for pattern formation which concerns on this Embodiment.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

(Overview)
First, the pattern forming laminate according to the present embodiment will be described. The laminate for pattern formation according to the present embodiment forms a desired pattern on a resin layer composed of a photosensitive resin.

  Here, the photosensitive resin constituting the resin layer is the same as that used in general photolithography.

  FIG. 1 is a schematic cross-sectional view showing a pattern forming laminate according to the present embodiment. As shown in FIG. 1A, a first base material (hereinafter also referred to as a base material B) 12 is formed on one main surface of a resin layer 11 (hereinafter also referred to as a resin layer A) in the laminate 10 for pattern formation. It is glued. A second base material 13 (hereinafter also referred to as a base material C) is bonded to the other main surface of the resin layer 11.

  When the pattern forming laminate 10 is exposed through a photomask (not shown) having a desired pattern, an unexposed portion 11a and an exposed portion 11b are formed in the resin layer 11 as shown in FIG. 1B. The

In the pattern-forming laminate 10 according to the present embodiment, in the unexposed portion 11a of the resin layer A, the adhesion between the resin layer A and the base material B (hereinafter referred to as F _(A-B1) ), The adhesion between the resin layer A and the substrate C (hereinafter referred to as F _(A-C1)) shows the following relationship.
F _(A-B1) > F _(A-C1)

At the same time, in the exposed portion 11b of the resin layer A, the adhesion between the resin layer A and the substrate B (hereinafter referred to as F _(A-B2)) and the adhesion between the resin layer A and the substrate C ( Hereinafter, F _(A-C2) ) represents the following relationship.
F _(A-B2) <F _(A-C2)

That is, when the unexposed portion 11a and the exposed portion 11b are formed by exposing the resin layer 11 in a desired pattern, the adhesion F _(A-B1) with the first base material 12 in the unexposed portion 11a is Adhesiveness F _(A-B2) with the 1st base material 12 becomes larger than adhesiveness F _(A-C1) with the 2nd base material 13, and in exposure part 11b of resin layer 11. It becomes smaller than the adhesiveness F _(A-C2) with the second substrate 13.

  Such a difference in adhesion can be realized, for example, by changing the material of the first base material 12 and the second base material 13 or by modifying the surface. The material of the base material will be described later.

  Examples of the surface modification method include baking, ultraviolet light irradiation, ozone treatment, corona discharge, and plasma. By these treatments, organic substances adhering to the surface can be removed, the chemical structure on the surface of the substrate, the state of glass or crystals, and the like can be changed.

  As a different surface modification method, there is a method in which another material is nano-ordered by spin coating, sputtering, vapor deposition or the like.

  For example, examples of the spin coat include silane coupling agents, chlorosilanes, and fluorine compounds. As silane coupling agents, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Diethyldimethoxysilane, diethyldiethoxysilane, triethylmethoxysilane, triethylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, Phenylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2 -Methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysila , Methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- ( 3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypro Pyrtriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilanesilane N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N- Phenyl-3-aminopropi Trimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, tri-i- And propylchlorosilane. These may be used singly or may be used as a mixture of plural kinds.

  Examples of the fluorine-based compound are compounds having one or more fluorine atoms, and are preferably compounds having an acidic group, a basic group, or a reactive group. Fluorine-containing groups include fluorine, difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl, 1,1,1,2, 3,3,3-heptafluoro-2-propyl, tetrafluoroethyleneoxy, hexafluoropropyleneoxy and the like. Examples of the acidic group include carboxylic acid, phenol group, phosphoric acid, phosphorous acid, and sulfuric acid group. Examples of the basic group include an amino group, a methylamino group, a dimethylamino group, and a pyridyl group. Examples of the reactive group include a hydroxy group, trialkoxysilyl group, dialkoxysilyl group, monoalkoxysilyl group, acryloxy group, vinyl group, allyl group, chlorosilyl group, acyl chloride group, and isocyanate group. Examples of commercially available release agents include OPTOOL DSX from Daikin Industries, Durasurf HD1101 and HD2101, Novec from Sumitomo 3M, trifluoromethyl (trimethoxy) silane, trifluoromethyl (triethoxy) silane, and the like. Can be mentioned.

  With the above-described configuration, it is possible to manufacture a substrate with a pattern as follows using the difference in adhesion between the first substrate 12 and the second substrate 13.

  When the first base material 12 and the second base material 13 are peeled off from each other, the unexposed portion 11a becomes the first base material 12 due to the difference in adhesion between the unexposed portion 11a and the exposed portion 11b as described above. And remains peeled off on the second base material 13 side. On the other hand, the exposed portion 11b remains adhered to the second base material 13, and peeling occurs on the first base material 12 side. As a result, a pattern composed of unexposed portions 11a is formed on the first base material 12 side, and a pattern composed of exposed portions 11b is formed on the second base material 13 side.

  Residues may remain where peeling occurs when they are peeled from each other. The residue refers to a residual resin having a thickness smaller than the initial thickness of the resin layer 11. The thickness of the residue is preferably less than half of the initial film thickness of the resin layer 11 and more preferably less than one-fifth because the process time can be shortened when it is later removed by ashing or short-time development. More preferably, it is 1/10 or less.

  The adhesion can also be measured with a peel tester or a tensile tester. As for the difference in adhesion, it is sufficient if there is a slight difference, but the adhesion (peeling force) can be measured with a tensile tester or the like. However, when the resin layer 11 is a thin film of 10 μm or less or is made of a viscous resin, it is difficult to measure the adhesion force. Therefore, it is only necessary that a difference in the adhesion force is obtained by actual exposure.

  Next, the manufacturing method of the pattern formation laminated body which concerns on this Embodiment, and the manufacturing method of the base material with a pattern using the laminated body for pattern formation are demonstrated. FIG. 2 is a schematic cross-sectional view showing each step of the manufacturing method of the pattern forming laminate and the manufacturing method of the substrate with pattern according to the present embodiment.

  As shown in FIG. 2A, first, a photosensitive resin material is applied on the surface of any one of the substrates, for example, the first substrate 12 to form the resin layer 11.

  Next, as shown in FIG. 2B, the second base material 13 is bonded to the surface of the resin layer 11 opposite to the first base material 12 to obtain the pattern forming laminate 10.

  The pattern forming laminate 10 thus obtained is subjected to an exposure process. As shown in FIG. 2C, a patterning mask 21 is disposed on the surface of the first base 12 opposite to the resin layer 11. The patterning mask 21 is provided with an exposure region 21 a that transmits light, for example, UV, and a non-exposure region 21 b that does not transmit UV. The exposure region 21 a is provided only in a part of the patterning mask 21.

  The patterning mask 21 may be brought into contact with the surface of the first substrate 12 or may be slightly separated.

  The resin layer 11 is exposed by irradiating UV through the patterning mask 21 as described above. Here, in order to expose the resin layer 11, one of the two base materials, in this example, the first base material 12 needs to be light transmissive, but is not particularly limited. The side where 21 is disposed, that is, the side on which UV is irradiated may be light transmissive.

  By exposure, the lower resin layer 11 of the exposure area 21a of the patterning mask 21 is exposed to form an exposed portion 11b, while the lower resin layer 11 of the non-exposed area 21b is not exposed and is not exposed. 11a is formed (see FIG. 1B).

  Thereafter, the first substrate 12 and the second substrate 13 are peeled off from each other. As a result, as shown in FIG. 2D, due to the difference in adhesion between the unexposed portion 11a and the exposed portion 11b as described above, the unexposed portion 11a remains adhered to the first substrate 12, and the second Peeling occurs on the substrate 13 side. On the other hand, the exposed portion 11b remains adhered to the second base material 13, and peeling occurs on the first base material 12 side. As a result, the pattern 22 composed of the unexposed portion 11a is formed on the first base material 12 side, and the pattern 23 composed of the exposed portion 11b is formed on the second base material 13 side. . As a result, patterned substrates 24 and 25 are obtained.

  As described above, if the laminate for pattern formation 10 according to the present embodiment is used, the resin layer can be easily patterned without a development process, so there is no fear of adversely affecting the environment or the human body. The number of steps can be reduced, and the patterned substrates 24 and 25 can be manufactured at low cost.

  For example, in the patterned substrate 24, a part of the exposed portion 11b may remain as a residue in the unexposed portion 11a, or in the patterned substrate 25, a portion of the exposed portion 11b may remain as a residue. In such a case, in order to remove the residue, it is also possible to remove the residue using a developer as in the conventional method. Compared with the conventional method because the amount of residue is small compared to the case of developing the unexposed part 11a or the exposed part 11b of the resin layer 11, the amount of the developer used is small and the development time is short. Thus, there is no fear of adversely affecting the environment and the human body, the number of processes can be reduced, and the patterned substrates 24 and 25 can be manufactured at low cost.

(Details)
Hereinafter, the pattern forming laminate according to the present embodiment will be described in more detail.

(Base material)
As a material of the 1st base material 12 and the 2nd base material 13, any of an organic material, an organic-inorganic hybrid material, or an inorganic material may be sufficient. The first substrate 12 and the second substrate 13 may be composed of a plurality of materials or a plurality of layers.

  For example, when there is a substrate as a support or cover film made of an organic material, specifically, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polychlorinated Block copolymer resin mainly composed of vinyl, polyethylene (PE), polypropylene (PP), polybutadiene, styrene-butadiene or styrene-isoprene, butadiene-styrene-methyl methacrylate copolymer resin, nylon, polyurethane, polyurethane / vinyl chloride Polymer, alkoxyalkyl (meth) acrylate copolymer, polyvinyl acetal, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene Examples include fluorinated polymers such as ethylene-ethylene copolymers, siloxane polymers such as polydimethylsiloxane, synthetic resins such as cellulose derivatives such as polyamide and rayon, cotton, hemp, pulp, woven fabric, knitted fabric, and nonwoven fabric. .

  Examples of the organic-inorganic hybrid material include a siloxane polymer having an organic group, a copolymer of an organic polymer and a siloxane unit, and an organic polymer in which fine particles such as silica, titania and zirconia are mixed.

  At least one of the first substrate 12 and the second substrate 13 may be made of an inorganic material and at least a part thereof. More specifically, an inorganic material may be formed on the organic material or the organic-inorganic hybrid material. The inorganic material layer may be on the resin layer 11 side or on the opposite side.

  Examples of the inorganic material include metals, metal oxides, metal nitrides, and semiconductor materials.

  The metal is preferably at least one selected from the group consisting of Al, Mo, Au, Ag, Cu and Ti.

Examples of the metal oxide include transparent conductors, silicon oxide (including SiO _2, alkali-free glass and quartz glass), aluminum oxide (including Al ₂ O ₃ and sapphire), titanium oxide (TiO ₂ ), and niobium oxide (Nb). ₂ O ₅ ), zirconium oxide (ZrO ₂ ), barium titanate (BaTiO ₃ ), strontium titanate (SrTiO ₃ ), and at least one selected from the group consisting of tantalum oxide (Ta ₂ O ₅ ). .

  Transparent conductors are ITO (tin doped indium tin oxide), IZO (zinc doped indium oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped tin oxide), TTO (tantalum doped oxide). It is preferably at least one selected from the group consisting of tin) and NTO (niobium doped titanium oxide), tin oxide, and zinc oxide.

  The semiconductor material is preferably a Si, SiC, Ge or III-V group compound.

The III-V group compound is preferably Si ₃ N ₄ , GaN, InN, AlN, GaP, InP, AlP, GaAs, InAs, AlAs, or the like.

  The above-mentioned inorganic material may be a base material alone, or a plurality of layers may be laminated.

  On the resin layer 11 side of at least one of the first base material 12 and the second base material 13, an organic material layer different from the material of the first base material 12 and the second base material 13, or an organic inorganic layer A hybrid material layer may be formed. When a single film or a self-supporting film cannot be produced, a substrate can be used as a support.

  As an organic material layer different from the material of the first base material 12 and the second base material 13 or an organic-inorganic hybrid material, a photo-curing resin can be used. By using a photocurable resin, it is possible to select a wide range of monomers and additives to be added, and a substrate having an arbitrary surface state can be produced.

  A photo-curing resin is one that has been polymerized and cured by radicals, acids, or bases generated by being activated by light, and has been cured by combining a reactive site activated by light with other molecules. . As light, light having an arbitrary wavelength can be used, but UV light is preferable.

  Preferable examples of the photocurable resin include fluorine-containing compounds and / or silicone-containing compounds.

  It is preferable that at least one of the first substrate 12 and the second substrate 13 transmits UV light necessary for exposure. The transmittance at 365 nm is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and most preferably 70% or more. In order to make a difference in contrast between the exposed portion 11b and the unexposed portion 11a, it is sufficient to transmit a little, but in order to make the contrast clearer, it is preferable that the transmittance is higher.

(Application to nano-implement method)
As for the 1st base material 12 and the 2nd base material 13, it is preferable that one side becomes the cover film side in a photosensitive dry film, and the other becomes a support body (base film) side. The cover film is a film that protects the resin layer 11 from being damaged.

  Furthermore, you may use the cover film side as a nanoimprint mold at the time of transferring an uneven | corrugated pattern to a transfer resin layer in the nanoimprint method. That is, the base material on the cover film side has a desired uneven structure.

  The concavo-convex structure may or may not be a periodic array, but is more preferably a periodic array.

  Examples of the concavo-convex structure include line and space (L / S), dots (convex or concave), squares (convex or concave), polygons (convex or concave), and the like.

  A material different from the photosensitive resin material constituting the resin layer 11 may exist in at least a part of the concave portion of the concave-convex structure.

  As the different materials, it is preferable to use different materials from the resin layer 11 such as optical properties such as refractive index and transmittance, physical properties such as dry etching resistance, elastic modulus and viscosity, and mechanical strength. For example, when materials having different physical properties with different dry etching resistance are used, when processing a base material laminated with a resin laminate, it can be processed into a shape having a two-step slope that is difficult to form alone.

  FIG. 3 is an explanatory diagram for explaining the concavo-convex structure in the pattern-forming laminate according to the present embodiment. For example, when the concavo-convex structure is dots, the dots 31 may be formed at a constant pitch P as shown in FIG. 3A, or a dot group 32 in which a plurality of dots 31 are combined as shown in FIG. 3B. Each dot 31 may be arranged so that has a certain periodicity.

  For example, the dots 31 may be arranged in a regular hexagonal arrangement, a hexagonal arrangement, a quasi-hexagonal arrangement, a quasi-tetragonal arrangement, a tetragonal arrangement, and a regular tetragonal arrangement. Further, all the dots 31 may not have periodicity, some of the dots 31 may be arranged to have periodicity, and the remaining dots 31 may be arranged at random.

  When the concavo-convex structure composed of dots (dot pattern) has periodicity, it is preferable because the in-plane uniformity of adhesion to the substrate is maintained. In addition, the lower limit of the distance (pitch P) between the dots 31 (between the nearest dots 31) is 50 nm or more from the viewpoint of embedding of the photosensitive resin material in the dot pattern and film thickness uniformity after application. Preferably, it is 100 nm or more, more preferably 150 nm or more. Further, the upper limit value of the pitch P is preferably 10,000 nm or less, more preferably 3000 nm or less, further preferably 2000 nm or less, and further preferably 1000 nm or less. As shown in FIG. 3A, the pitch P indicates the distance between the vertices or centers of the closest dots.

  The thickness of the resin layer 11 can be set to a desired thickness.

  The lower limit of the width of each dot 31 is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more from the viewpoint of embedding of the photosensitive resin material in the dot pattern and film thickness uniformity after application. 300 nm or more is most preferable. The upper limit of the width is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 700 nm or less, and most preferably 500 nm or less. The width of the dot 31 indicates the width of the bottom of the dot 31 when the dot 31 is a convex portion, and indicates the opening width when the dot 31 is a concave portion.

  The dots 31 constituting the concavo-convex structure may be convex portions or concave portions, and the shape of the dots 31 depends on the design of the resin mold to be used.

  The optimum shape and size of the concavo-convex dot 31 can be variously selected depending on the refractive index of the material used, ashing resistance, etching resistance, optical characteristics such as light extraction improvement, physical characteristics, and the like.

  In addition, when the laminate 10 for pattern formation is applied to the nanoimprint method, in order to make a difference in adhesion between the first substrate 12 and the second substrate 13, one substrate is A substrate coated with a compound containing a siloxane polymer such as polydimethylsiloxane and a fluorine compound, a substrate having a resin layer containing a siloxane polymer such as polydimethylsiloxane and a fluorine compound, or polydimethylsiloxane A base material containing a siloxane polymer and a fluorine-based compound is more preferable. It suffices if these compounds are present in the portion in contact with the resin layer 11. When other materials are used as a master mold, a mold release treatment may be performed using a fluorine compound or a silicon compound.

  In the following description, a case where the pattern forming laminate 10 according to the present embodiment is applied to the nanoimprint method will be described.

(Resin layer)
As the photosensitive resin material constituting the resin layer 11, a compound that generates an active substance in response to light, such as a photopolymerization initiator, a photoacid generator, or a photobase generator, can be used. Preferably, a photopolymerization initiator is preferable from the viewpoint of the reactivity of the photosensitive compound to light and the reactivity of the active substance generated from the photosensitive compound.

  The photosensitive resin material may be an inorganic material or an organic material. Inorganic materials are preferable from the viewpoints of durability such as heat resistance and light resistance, etching resistance, and transparency, and organic materials and organic-inorganic hybrid materials can be selected from various materials and solvents when forming the resin layer 11. To preferred. Furthermore, by using an organic material, it is easy to process the substrate itself by ashing or etching. The resin layer 11 may be composed of a plurality of materials or a plurality of layers.

<Photosensitive resin material using photopolymerization initiator>
Examples of the photosensitive resin material using the photopolymerization initiator include an ethylenically unsaturated addition polymerizable monomer-containing composition. Preferable photopolymerization initiators are compounds that generate radicals by light, and include the following compounds.

  (1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone

  (2) Acetophenone derivatives: For example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, Irgacure (Registered trademark) 651), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, Irgacure 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF, Irgacure 907), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one (manufactured by BASF, Irgacure 127), phenylglyoxyl Methyl acid

  (3) Thioxanthone derivatives: for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone

  (4) Benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal

  (5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF, Darocur (registered trademark) 1173)

  (6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (Iracacure OXE01 manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylben) Yl) -9H- carbazol-3-yl] -, 1- (O- acetyloxime) (BASF Corp., IrgacureOXE02)

  (7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane

  (8) α-aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, Irgacure 369), 2-dimethylamino-2- (4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (Irgacure 379, manufactured by BASF)

  (9) Phosphine oxide compounds: For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, Irgacure 819), bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, Darocur (registered trademark) TPO)

  (10) Titanocene compound: for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (manufactured by BASF) , Irgacure 784)

  Moreover, when using these photoinitiators, it may be individual or a mixture of 2 or more types.

  Among the photopolymerization initiators, the benzoin derivative of (5) or the phosphine oxide compound of (9) is more preferable particularly from the viewpoint of photosensitivity, and from the viewpoint of stability to light, (1) A benzophenone derivative, an acetophenone derivative of (2), or an α-hydroxyketone compound of (7) is preferred. The addition amount is 0.01 to 30 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass with respect to the acrylic / methacrylic compound (100 parts by mass). And more preferably 0.3 to 1.5 parts by mass. When applying the pattern forming method according to the present embodiment to the nanoimprint method, the addition amount of the photopolymerization initiator is 0.01 parts by mass or more from the viewpoint of obtaining a fine uneven structure with practical hardness, and the composition From the viewpoint of stability of the product, it is preferably 30 parts by mass or less.

  The photosensitive resin material preferably contains an ethylenically unsaturated addition polymerizable monomer (hereinafter also referred to as “acrylic monomer”). As the acrylic monomer added to the photosensitive resin material, it is preferable to use a compound containing an acryloyl group or a methacryloyl group from the viewpoint of improving etching resistance, hardness and heat resistance.

  From the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance, it is preferable that a monomer containing an aromatic group, a polycyclic group, or a heterocyclic group is included in the photosensitive resin material (one compound is Some compounds are classified into two or more of aromatic groups, polycyclic groups, and heterocyclic groups). Examples of the aromatic group include a compound having a phenyl, naphthalene, or anthracene skeleton. The skeleton containing a phenyl group includes a compound in which a plurality of aromatic groups such as biphenyl are directly bonded to each other, and a plurality of aromatic groups such as bisphenol A skeleton are carbon, oxygen, nitrogen, silicon and sulfur. A compound bonded with a crosslinking group including at least one of them.

Examples of compounds to which an aromatic group is added include phenyl, naphthalene, and anthracene as substituents: —R ₁ —O (C═O) —CR ₂ ═CH ₂ group (R ₁ is carbon, oxygen, nitrogen, A substituent containing at least one element of silicon and sulfur, preferably a substituent composed of carbon and / or oxygen, and R ₂ is hydrogen or a methyl group. Things. Specific examples thereof include phenyl acrylate, phenyl methacrylate, 1-naphthalene acrylate, 1-naphthalene methacrylate, 2-naphthalene acrylate, 2-naphthalene methacrylate, 1-anthracene acrylate, 1-anthracene methacrylate, 2-anthracene acrylate, 2- Anthracene methacrylate, 9-anthracene acrylate, 9-anthracene methacrylate and the like can be mentioned. As a substituent for phenyl, naphthalene and anthracene, a plurality of acryloyl groups or methacryloyl groups may be bonded to these compounds. Further, a structure in which another hydrogen atom is substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine, or iodine may be used. Development with an aqueous alkali solution is possible when such a compound has a substituent such as a carboxylic acid group, a carboxylic acid anhydride group, or a hydroxy group that improves the solubility in an aqueous alkali solution. Therefore, it is preferable.

  Examples of the compound in which a plurality of aromatic groups are directly bonded include at least one of compound group A including the following structure A.

  Examples of the compound in which a plurality of aromatic groups are bonded with a bridging group containing at least one of carbon, oxygen, nitrogen, silicon, and sulfur include at least one of compound groups B including the following structure B.

  Examples of the polycyclic compound include at least one of the compound group C including the following structure C.

  Examples of the heterocyclic compound include at least one of compound group D including the following structure D.

  The substitution position of the aromatic group, polycyclic group, or heterocyclic group may be substituted anywhere as long as it can be bonded, or may be substituted in plural.

  As mentioned above, good acrylic monomers such as ashing resistance, etching resistance, heat resistance, etc. are mentioned, but it is sufficient that the composition as a whole contains an aromatic group, a polycyclic group, or a heterocyclic group. An acrylate monomer or an acrylic monomer having an ethylene oxide chain may be added.

  The addition amount is an aromatic group, polycyclic group or heterocyclic group-containing monomer with respect to the acrylic monomer compound (100 parts by mass) from the viewpoints of ashing resistance, etching resistance, film strength, hardness, and heat resistance. It is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and most preferably 70 parts by mass or more.

  An oligomer or polymer may be added to the resin material for viscosity adjustment, ashing resistance, and etching resistance. As the oligomer or polymer to be added, it is more preferable to use an oligomer or polymer having an acryloyl group or a methacryloyl group.

  Preferred structures include the above-described phenol novolac oligomer / polymer, cresol novolac oligomer / polymer, styrene oligomer / polymer, norbornene ring-opening polymer oligomer / polymer, norbornene addition polymer oligomer / polymer, norbornadiene ring opening. Polymer oligomers / polymers, norbornadiene addition polymer oligomers / polymers, oligomers / polymers of the above acrylic monomers, and the like. Furthermore, it is preferable that an acryloyl group or a methacryloyl group is bonded to the side chain of the oligomer / polymer because physical properties such as ashing resistance, etching resistance and hardness are further improved. In addition, if the side chains of these oligomers / polymers have a substituent such as a carboxylic acid group, a carboxylic anhydride group or a hydroxy group that improves the solubility in an alkaline aqueous solution, development with an alkaline aqueous solution is possible. Therefore, it is preferable.

  The addition amount is preferably 10 parts by mass or more and 20 parts by mass or more with respect to the acrylic monomer compound (100 parts by mass) from the viewpoints of ashing resistance, etching resistance, film strength, hardness, and heat resistance. More preferably, it is more preferably 30 parts by mass or more, from the viewpoint of curability of the composition, it is preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less.

  Moreover, an inorganic material and an organic-inorganic hybrid material can be used from a viewpoint of ashing resistance, etching resistance, heat resistance, and transparency. Alternatively, an inorganic material or an organic-inorganic hybrid material can be added to the organic material.

  As an inorganic material, sol-gel material and an inorganic filler (inorganic fine particle) can be included, for example. Moreover, as an inorganic material, you may be comprised only with sol-gel material. Examples of inorganic materials include inorganic oxides such as silica, titania, zirconia, and zinc oxide, metal composite oxides such as barium titanate, strontium titanate, and ITO, and metals such as gold, silver, copper, aluminum, and chromium. It is done.

  Moreover, it is preferable to contain at least one element selected from Al, Si, P, Ti, Ga, Ge, Zr, Nb, Ta, In, and Sn. In particular, Ti, Zr, and Si are preferable.

  As the organic-inorganic hybrid material, metal alkoxides, metal chlorides, and their hydrolysates and hydrolysis condensates may be used. From the viewpoint of crack resistance and stability, it is preferable to use a condensate.

  Examples of the metal alkoxide include silane alkoxide, titanium alkoxide, zirconium alkoxide, and tantalum alkoxide. From the viewpoint of stability, silane alkoxide, titanium alkoxide, or zirconium alkoxide is preferable, and silane alkoxide is more preferable. Examples of the metal chloride include tetrachlorosilane, titanium chloride, zirconium chloride, and tantalum chloride.

  Examples of the silane alkoxide or chlorosilane include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and vinyltrimethoxy. Silane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, di Cyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldimethoxysila , Diphenyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxy Silane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acrylic Roxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysila , Acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ) Ethylethoxydimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Triethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) ) -2-Aminoethyl-3-a Nopropyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, Examples thereof include dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, and tri-i-propylchlorosilane.

  From the viewpoint of the stability, hardness, ashing resistance, and etching resistance of the cured product, it preferably has a functional group capable of reacting with a photopolymerization initiator, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl. Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2 -Methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacrylo Shi methyl dimethoxy silane, acryloxymethyl trimethoxy silane, include acryloxymethyl triethoxysilane.

  Other metal alkoxides or metal chlorides include titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, tantalum pentamethoxide, tantalum pentaethoxide, tantalum penta n-propoxide, tantalum pentaisopropoxide, tantalum penta n-butoxide, etc. It is done.

  Fine particles such as titanium oxide, zirconium oxide, silica, ITO, ZnO, SnO, IZO, ATO, and AZO may be contained. In that case, from the viewpoint of film physical properties and transparency, the particle size is preferably 1000 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. These may be used alone or in combination of two or more.

  For the purpose of improving or controlling the etching resistance and ashing resistance of the composition, when a metal oxide, a metal composite oxide, a metal, or an organic-inorganic hybrid material is added, a dot composed of a plurality of convex portions or concave portions is added. It is necessary to mix in a balanced manner throughout the composition in the concavo-convex structure to be included. On the other hand, in order to improve physical properties such as heat resistance and transparency, the addition amount is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to the composition (100 parts by mass) of the photosensitive resin material. More preferably, it is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and most preferably 90 parts by mass or more.

<Photosensitive resin material using photoacid generator>
The photoacid generator is not particularly limited as long as it generates a photoacid by light irradiation. Examples thereof include aromatic onium salts such as sulfonium salts and iodonium salts. Examples of the photoacid generator include sulfonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, benzoin tosylate, adekatopomer ( (Registered trademark) sp-170 (manufactured by ADEKA), ADEKA OPTMER (registered trademark) sp-172 (manufactured by ADEKA), WPAG-145 (manufactured by Wako Pure Chemical Industries), WPAG-170 (manufactured by Wako Pure Chemical Industries, Ltd.) ), WPAG-199 (made by Wako Pure Chemical Industries), WPAG-281 (made by Wako Pure Chemical Industries), WPAG-336 (made by Wako Pure Chemical Industries), WPAG-367 (made by Wako Pure Chemical Industries), CPI-100P San Apro), CPI-101A (San Apro), CPI-200K (San Apro), CPI-210S (San Apro), DTS-102 (Midori Kagaku), TPS-TF (Toyo Gosei Co., Ltd.) And DTBPI-PFBS (manufactured by Toyo Gosei Co., Ltd.).

  The addition amount of a photo-acid generator is 0.01-30 mass parts with respect to a cationic curable monomer compound (100 mass parts), Preferably it is 0.1-20 mass parts, More preferably, it is 0.00. It is 2-10 mass parts, More preferably, it is 0.3-5 mass parts. From the viewpoint of obtaining a dot pattern having a practical hardness, the addition amount of the photoacid generator is 0.01 parts by mass or more, and from the viewpoint of the stability of the composition, it is 30 parts by mass or less.

  It is preferable to add a cationic curable monomer and / or polymer to the photoacid generator composition.

  From the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance, it is preferable that a monomer containing an aromatic group, a polycyclic group, or a heterocyclic group is included in the photosensitive resin material (one compound is Some compounds are classified into two or more of aromatic groups, polycyclic groups, and heterocyclic groups). Examples of the aromatic group include a compound having a phenyl, naphthalene, or anthracene skeleton. As the skeleton containing a phenyl group, a compound in which a plurality of aromatic groups such as biphenyl are directly bonded to each other, and a plurality of aromatic groups such as a bisphenol A skeleton are carbon, oxygen, nitrogen, silicon, and sulfur. Among them, a compound bonded with a crosslinking group including at least one kind is included.

Examples where the aromatic group is attached include phenyl, naphthalene, and anthracene as substituents —R ₁ —R ₄ (R ₁ represents at least one element of carbon, oxygen, nitrogen, silicon, and sulfur). And a substituent composed of carbon and / or oxygen, and R ₄ is an epoxycyclohexyl group, a glycidyl group, or a vinyl ether group). Another hydrogen atom may be substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine or iodine. In addition, if the compound has a substituent such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improves the solubility in an alkaline aqueous solution, the development in the alkaline aqueous solution can be performed. It is preferable to make it possible.

  Examples of the compound in which a plurality of aromatic groups are directly bonded include at least one of the compound group A.

  Examples of the compound in which a plurality of aromatic groups are bonded with a bridging group containing at least one of carbon, oxygen, nitrogen, silicon, and sulfur include at least one of the compound group B.

  Examples of the polycyclic compound include at least one of the compound group C.

  Examples of the heterocyclic compound include at least one of the compounds D described above.

  As a substitution position of the above-mentioned aromatic group, polycyclic group, or heterocyclic group, it may be substituted anywhere as long as it can be bonded, and a plurality of substitution positions may be substituted.

  As mentioned above, good acrylic monomers such as ashing resistance, etching resistance, heat resistance and the like have been mentioned, but it is sufficient that the entire composition contains an aromatic group, a polycyclic group, or a heterocyclic group. Or a cationic curable monomer having an ethylene oxide chain may be added.

  Specific examples of the cationic curable monomer include the following. Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylic acid-3,4-epoxy. Examples include -6′-cyclohexylmethyl, vinylcyclohexylene monooxide 1,2-epoxy-4-vinylcyclohexane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the glycidyl ether include bisphenol A glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, Examples include methylolpropane triglycidyl ether, glycidyl methacrylate, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

  Examples of the oxetane compound include 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3allyloxymethyloxetane, 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane.

  Examples of the vinyl ether include 2-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and 1,4-butanediol divinyl ether. It is done.

  Among these, an alicyclic epoxy compound improves polymerization initiation rate, and an oxetane compound has an effect of improving the polymerization rate. Therefore, it is preferable to use alicyclic epoxy compound, and glycidyl ether reduces the viscosity of a cation-curable resin material. Since it is effective in workability, it is preferable to use it. More preferably, from the viewpoint of increasing the reaction rate of the initial reaction and the initial stage of the reaction, the alicyclic epoxy compound and the oxetane compound are used in combination, and more preferably the weight ratio of the alicyclic epoxy compound and the oxetane compound is It is to use together in the range of 99: 1 to 51:49. From the viewpoint of increasing the heat resistance of the cured product, an inorganic compound such as Si or Ti atom is preferably included.

  The addition amount is the above aromatic group, polycyclic group, or heterocyclic group with respect to the cationic curable monomer compound (100 parts by mass) from the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance. The content monomer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and most preferably 70 parts by mass or more.

  In order to adjust viscosity, ashing resistance, and etching resistance, an oligomer or polymer may be added to the resin material in the same manner as the photosensitive resin material using the above-described photopolymerization initiator.

  For the purpose of improving or controlling the etching resistance and ashing resistance of the composition, when a metal oxide, a metal composite oxide, a metal, or an organic-inorganic hybrid material is added, a dot composed of a plurality of convex portions or concave portions is added. It is necessary to blend in a balanced manner throughout the composition in the included microstructure layer. On the other hand, in order to improve physical properties such as heat resistance and transparency, the addition amount is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to the composition (100 parts by mass) of the microstructure layer. More preferably, it is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and most preferably 90 parts by mass or more.

<Photosensitive resin material using photobase generator>
The photobase generator is not particularly limited as long as it generates a base by light irradiation. For example, WPBG-018 (manufactured by Wako Pure Chemical Industries), WPBG-027 (manufactured by Wako Pure Chemical Industries), WPBG-082 (manufactured by Wako Pure Chemical Industries), WPBG-140 (manufactured by Wako Pure Chemical Industries), etc. Is mentioned.

  As the reactive monomer used in the photosensitive resin material using the photobase generator, an epoxy group, an oxetane group, a metal alkoxide, a hydrolyzate thereof, a hydrolysis condensate, and the like can be used.

  The addition amount of a photobase generator is 0.01-30 mass parts with respect to a reactive monomer compound (100 mass parts), Preferably it is 0.1-20 mass parts, More preferably, it is 0.2. -10 parts by mass, more preferably 0.3-5 parts by mass. From the viewpoint of obtaining a dot pattern having a practical hardness, the addition amount of the photoacid generator is 0.01 parts by mass or more, and from the viewpoint of the stability of the composition, it is 30 parts by mass or less.

(Laminated structure)
The resin layer 11 may have a structure in which a plurality of resin layers are sequentially stacked. When the ashing and etching steps are performed, it is preferable to use a resin layer 11 having excellent ashing resistance on the surface (dot pattern surface) side and a material having excellent etching resistance on the side opposite to the surface. For example, a photosensitive resin material containing a titanium compound is used on the surface side of the resin layer 11, and a photosensitive resin material having a high carbon ratio is used on the opposite surface side of the resin layer 11.

(Organic solvent)
The following organic solvent may be contained in the photosensitive resin material.
(1) Aliphatic alcohol: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, 2-octanol, 3-octanol, 1-nonanol, isononyl alcohol, 3, 5, 5 -Trimethyl hex Nord, 1-decanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-Hendekanoru, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, Hekishinoru

  (2) Aromatic alcohol: benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4 -Hydroxy-3-methoxyphenyl) methanol, (3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol 2- (4-hydroxy-3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropane-2 -Ol, cinnamyl alcohol, 3- (4- Loxy-3-methoxyphenyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-methoxyphenyl) prop-2-en-1-ol, diphenylmethanol, trityl alcohol, 1,2 -Diphenylethane-1,2-diol, 1,1,2,2-tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3-dimethanol, benzene-1, 4-dimethanol

  (3) Alicyclic alcohol: cyclohexanol, methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydro-2-furanmethanol

  (4) Glycol and derivatives thereof: for example, ethylene glycol, ethylene glycol monoalkyl (1 to 8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (1 to 6 carbon atoms) ) Ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, Propylene glycol monoalkyl (1 to 4 carbon atoms) ether, propylene glycol monophenyl Ether, dipropylene glycol monoalkyl (1-3 carbon atoms) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate

  (5) Ketone compounds: acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl n-butyl ketone, methyl isobutyl Ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2-octanone, 3- Octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutyl ketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone Isophorone

  (6) Others: N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, γ-butyrolactone, α-acetyl-γ- Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone

  These organic solvents can be used alone or in combination of two or more. Among these, acetone, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable.

  These organic solvents can be appropriately added to the photosensitive resin material depending on the coating film thickness and viscosity, but are 50 to 10,000 mass% based on the mass of all components other than the solvent in the photosensitive resin material. It is preferable to use in the range.

(Other additives)
The photosensitive resin material may contain an ultraviolet absorber, a light stabilizer, an adhesion assistant, a polymerization inhibitor, a sensitizer, an antioxidant, or a smoothness imparting agent.

(composition)
From the viewpoint of ashing resistance and etching resistance, the photosensitive resin material preferably has a large ratio of the number of carbon atoms in the total number of atoms contained in the photosensitive resin material.

(Method for producing pattern forming laminate)
Hereinafter, the pattern forming laminate according to the present embodiment will be described in more detail. As shown in FIG. 2A, first, a photosensitive resin material is applied to one first base material 12 to form a resin layer 11. Next, as shown in FIG. 2B, the resin layer 11 is bonded to the other second base material 13.

  As a coating method, spin coating, bar coating, dip, spray coating, die coating, gravure coating, gravure offset, or the like can be used. From the viewpoint of in-plane uniformity and large area coating, it is preferable to use spin coating, bar coating, die coating, or gravure coating. In the case where there is a concavo-convex structure on the first substrate 12 side, it is preferable to use a bar coat or a die coat from the viewpoint of filling the concavo-convex shape.

  In the case of spin coating, depending on the solid content or viscosity of the photosensitive resin material, from the viewpoint of film thickness uniformity, the main rotational speed is preferably 300 rpm or more, more preferably 500 rpm or more, further preferably 1000 rpm or more, 1500 rpm or more is most preferable. In addition, 5000 rpm or less is preferable from the viewpoint of safety during application. The main rotation time is preferably 3 seconds or more, more preferably 5 seconds or more, and even more preferably 10 seconds or more.

  In the case of bar coating or die coating, depending on the solid content or viscosity of the photosensitive resin material, from the viewpoint of film thickness uniformity, the coating wet film thickness is preferably 1 μm or more, more preferably 2 μm or more, and more preferably 3 μm or more. More preferably, it is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

  After applying the photosensitive resin material to the first base material 12, it may be heated and dried in order to remove the organic solvent or to improve the adhesion to the first base material 12.

  When applied by spin coating, although depending on the number of rotations and time, the organic solvent may have already been removed to some extent, so the solvent can be removed by leaving it at room temperature for several tens of seconds to several hours. Good.

  When heating and drying, although it depends on the type of solvent used and the amount of residual solvent, it is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher. In particular, when the first substrate 12 is made of a resin, in order to apply the photosensitive resin material with a uniform film thickness and stably hold the photosensitive resin material on the first substrate 12, 200. ° C or lower is preferable, and 150 ° C or lower is preferable. Although it depends on the drying temperature, the drying time is preferably 1 minute or more, more preferably 3 minutes or more, and further preferably 5 minutes or more.

  You may pressurize when bonding the resin layer 11 to the 2nd base material 13. FIG. The pressure at the time of pressurization depends on the physical properties and state of the photosensitive resin material (for example, a dry state). This is preferable because contamination is minimized. Moreover, when the 2nd base material 13 by the side of bonding has an uneven structure, it is more preferable to pressurize from a viewpoint of filling of the photosensitive resin material in an uneven structure.

  Moreover, you may heat at the time of bonding. The object to be heated may be a bonding atmosphere or the first base material 12 and / or the second base material 13, but from the viewpoint of simplicity in process, It is preferable to heat the second base material 13. By heating, adhesion with the photosensitive resin material can be improved and air entrainment at the time of bonding can be minimized.

As the shape of the exposure region 21a or the non-exposure region 21b of the patterning mask 21, any shape such as a circle, a square, a rectangle, a trapezoid, a line and space, or the like can be used. The shape may be a blank pattern (exposed photosensitive resin material exposed to the shape) or a remaining pattern (exposed photosensitive resin material inside the shape). The area of their shape, in terms of patterning accuracy, preferably 1 [mu] m ² or more, more preferably 1 [mu] m ² or more, more preferably 25 [mu] m ² or more, more preferably 100 [mu] m ² or more, 400 [mu] m ² or more is most preferred.

  The exposure may be any one of a reduction projection method, an equal magnification projection method, contact exposure, and proximity exposure. The reduction projection method is preferable from the viewpoint of patterning accuracy, and contact exposure or proximity exposure is preferable from the viewpoint of throughput.

  When a fine concavo-convex structure exists on the surface of the first substrate 12, light may be scattered due to a difference in refractive index between the first substrate 12 and the photosensitive resin material. In such a case, from the viewpoint of patterning accuracy, a reduction projection method, an equal magnification projection method, or contact exposure is preferable. If a projection method or proximity exposure that does not cause the mask to be soiled by contact with the mask is used, the cost of the mask can be reduced.

The exposure amount, it is possible to change the optimal value by adding the amount of active substance to be added to the photosensitive resin material, from the viewpoint of the process throughput, is preferably 3000 mJ / cm ² or less, 2000 mJ / cm ² The following is more preferable, and 1000 mJ / cm 2 or less is more preferable. Further, from the viewpoint of process reproducibility, 10 mJ / cm 2 or more is preferable, 20 mJ / cm ² or more is more preferable, and 50 mJ / cm ² or more is more preferable.

  It is preferable to heat the pattern forming laminate 10 after the exposure. By heating, the active substance generated by the exposure is further activated, and the contrast between the exposed portion 11b and the unexposed portion 11a can be increased. The heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 80 ° C. or higher from the viewpoint of activation of the active substance. On the other hand, from the stability of the 1st base material 12 and the 2nd base material 13, and the stability of a dot pattern, 200 ° C or less is preferred and 150 ° C or less is more preferred.

  The heating time depends on the heating temperature, but is preferably 5 seconds or more from the viewpoint of process stability, more preferably 10 seconds or more, and preferably 10 minutes or less from the viewpoint of throughput.

  Subsequently, one first substrate 12 is peeled from the pattern forming laminate 10. In the peeling step, the peeling direction may be the same as or different from the direction at the time of bonding. From the viewpoint of throughput, the peeling speed is preferably 0.1 cm or more, more preferably 0.5 cm or more, and further preferably 2.0 cm or more.

  After peeling, the unexposed portion 11a adheres to the first substrate 12 side, and the exposed portion 11b adheres to the other second substrate 13 side. A part (residue) of the exposed part 11b may remain on the first base material 12 to which the unexposed part 11a is adhered, or a part of the unexposed part 11a to the second base material 13 to which the exposed part 11b is adhered. May remain.

  If you want to remove it completely, you can remove it with a developer as in the conventional method, but since the remaining amount is less than when all remains, the development time can be shortened. The development conditions can be relaxed.

  Examples of the developing method include dip, dispense spin, spray, shower and the like. Examples of the developer include organic solvents, alkaline aqueous solutions, and acidic aqueous solutions. From the viewpoint of influence on the first substrate 12 and the second substrate 13, an organic solvent or an alkaline aqueous solution is preferable. Further, an alkaline aqueous solution is more preferable from the viewpoint of environmental harmony and safety.

  The organic solvent used as the developer may be any organic solvent that dissolves the components in the photosensitive resin material. From the viewpoint of boiling point and flash point, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, gamma Examples include butyrolactone.

  After developing with a developing solution, it may be rinsed with a low-boiling organic solvent. For example, acetone, ethanol, methanol, isopropanol, etc. are mentioned.

  After developing with a solvent, it may be rinsed with water. By rinsing with water, it is possible to prevent elution of the finely dissolved component in the developer in the exposed area.

  Examples of suitable alkaline aqueous solutions include, for example, ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like. And amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine. In particular, weak carbonate containing 0.05 to 10% by mass of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine. Development is preferably performed using an alkaline aqueous solution.

  When developing with an alkaline aqueous solution, it is preferable to use pure water as the rinsing liquid. Development and rinsing are preferably performed at a temperature of 20 ° C. or higher and 35 ° C. or lower.

  You may heat after image development and / or rinse. By heating, the developing solution and the rinsing solution that have penetrated into the pattern can be removed. In addition, the photosensitive resin material can be further cured.

  Further, as another method, it can be removed by ashing or the like.

In the pattern forming laminate 10 after the exposure, the size of the plurality of regions independent constituting the exposed portion 11b or unexposed portion 11a is at least one of 25μm ² ~1000000μm ² about.

  For the adhesion and adhesion between the first substrate 12 and the second substrate 13 and the photosensitive resin material before and after exposure, the peel strength is measured by a surface interface property analyzer (SAICAS) or a measuring device such as Tensilon. It is possible to measure. From the result, it is possible to design the type of each of the first base material 12 and the second base material 13 and the structure of the compound of the photosensitive resin material constituting the resin layer 11.

(Optical substrate, optical element)
The layered body 10 for pattern formation according to the present embodiment is used to form a concavo-convex structure on a III-V group compound such as sapphire, GaN, GaAs, GaP, or a transparent electrode such as ITO in an optical element, for example, an LED. be able to.

  When a fine concavo-convex structure is formed on at least a part of the surface in contact with the resin layer (A) of the base material (B) or the base material (C), the fine concavo-convex structure appears on the surface of the pattern after the pattern is formed. . By processing the patterning substrate having this fine concavo-convex structure by ashing, dry etching, wet etching or the like, it is possible to form the fine concavo-convex structure in a part of the optical element. In dry etching, fluorine gas or chlorine gas can be used as a gas to be used.

  As described above, according to the pattern forming laminate 10 according to the present exemplary embodiment, the first base material 12 and the second base material 13 of the unexposed portion 11a and the exposed portion 11b of the resin layer 11 are provided. By utilizing the difference in adhesion to each of them, the resin layer 11 can be easily patterned without a development step, and the pattern can be easily formed on the optical base material. Can be manufactured.

  Hereinafter, the present invention will be described in more detail based on examples carried out to clarify the effects of the present invention. In addition, the material in the following Example, use composition, a process process, etc. are illustrations, and can be changed and implemented suitably. Other modifications can be made without departing from the scope of the present invention. Therefore, the present invention is not limited at all by the following examples.

<Preparation of base material>
A first base material (side to which the unexposed portion is bonded) was prepared as follows.
First, a resin composition (Ia) containing the following fluorine compound is prepared on a PET film, applied, sandwiched between different PET films, and exposed to 1000 mJ / cm ² , then one PET film is peeled off, A base material (A) was produced.

  Resin composition (Ia): 17.5 parts by mass of OPTOOL DAC HP (manufactured by Daikin Industries, Ltd., fluorine-based other functional monomer), 100 parts by mass of trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M350), (1- Hydroxycyclohexyl) phenyl ketone (BASF, Irgacure 184) 5.5 parts by mass and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (BASF, Irgacure 369) 2 0.0 part by weight of the mixture.

As a base material (B) having a concavo-convex structure, a substrate having a dot pattern consisting of the following concave portions on the surface was prepared.
(Dot pattern)
Concave diameter: 650 nm
Concave depth: 800 nm
Pitch Px in the X axis direction: 700 nm
Y-axis direction pitch Py: 700 nm

  A substrate having a concavo-convex structure is produced by producing a mold for producing a resin mold having a fine dot pattern by a direct drawing lithography method using a semiconductor pulse laser, and further through a transfer step using the resin composition (Ia). A material (B) was produced.

  In the method for producing the substrate (B), a substrate (C) was produced using the resin composition (Ib) instead of the resin composition (Ia).

  Resin composition (Ib): 5.5 parts by mass of OPTOOL DAC HP (produced by Daikin Industries, Ltd., fluorine-based other functional monomer), 100 parts by mass of trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., M350), (1- Hydroxycyclohexyl) phenyl ketone (BASF, Irgacure 184) 5.5 parts by mass and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (BASF, Irgacure 369) 2 0.0 part by weight of the mixture.

[Production Example 1]
The following photosensitive resin material (II) was prepared, and the photosensitive resin material (II) was applied onto the base material (A) using a bar coater (No. 4) to obtain a sheet (1). The sheet (1) was dried in an oven at 105 ° C. for 15 minutes. Thereafter, the sheet (1) is laminated on a quartz substrate on which ITO is formed as a second substrate (the side to which the exposed portion is bonded), which has been heated to 85 ° C. in advance, and laminated. The body (A-1) was obtained.

  Photosensitive resin material (II): CNEA-100 (manufactured by KS Corporation, novolak acrylate solid content 50%) 30 parts by mass, 9,9′-bis (4- (acryloxyethoxy) phenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) EA-HG001) 4.0 parts by mass, Irgacure 184 (BASF) 0.44 parts, Irgacure 369 (BASF) 0.16 parts and propylene glycol monomethyl ether (PGME) 62 parts, acetone 42 parts Mixture of.

[Production Example 2]
A laminate was produced in the same manner as in Production Example 1, but the laminate (A-2) was obtained using the second substrate (the side to which the exposed portion is bonded) as the quartz substrate.

[Production Example 3]
Although the laminated body was produced by the method similar to the manufacture example 1, using the base material (B) instead of a base material (A) as a 1st base material, the photosensitive resin laminated body (B-1) is used. Obtained.

[Production Example 4]
Although the laminated body was produced by the method similar to the manufacture example 2, using the base material (B) instead of the base material (A) as a 1st base material, the photosensitive resin laminated body (B-2) is used. Obtained.

[Production Example 5]
The following photosensitive resin material (III) was prepared, and the photosensitive resin material (III) was applied onto the base material (A) using a bar coater (No. 4) to obtain a sheet (2). The sheet (2) was dried in an oven at 105 ° C. for 10 minutes. Photosensitive resin material (II) was further applied to the obtained sheet (2) using a bar coater (No. 4) to obtain a sheet (3). The sheet (3) was dried in an oven at 105 ° C. for 15 minutes. The sheet (3) was bonded to a quartz substrate on which ITO was formed as a second substrate (side to which the exposed portion was bonded) that had been heated to 85 ° C. in advance, and the laminate (B- 3) was obtained.

  Photosensitive resin material (III): 11 parts by mass of tetra-n-butoxy titanium (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.8 parts by mass of 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), trimethyl-terminated phenylmethylsiloxane (Toray Dow Corning, SH710) 0.84 parts by weight, Irgacure 184 (BASF) 0.33 parts, Irgacure 369 (BASF) 0.12 parts, propylene glycol monomethyl ether (PGME) 20 parts, A mixture of 82 parts by weight of acetone.

[Production Example 6]
A laminate was produced in the same manner as in Production Example 5, but a laminate (B-4) was obtained using a quartz substrate as the second substrate (the side to which the exposed portion is bonded).

[Production Example 7]
Although the laminated body was produced by the method similar to the manufacture example 2, the laminated body (C-1) was obtained using the base material (C) instead of the base material (A). A Teflon (registered trademark) plate was used as the substrate (C).

  The laminates obtained in Production Examples 1 to 7 are summarized in Table 1 below.

  Subsequently, patterning was performed in the following Examples 1 to 6 and Comparative Example 1 using the laminate shown in Table 1.

[Example 1]
A patterning mask was placed on the substrate (A) of the laminate A-1 and contact exposure was performed using a parallel light exposure machine. The illuminance was 5.0 mW / cm ² and the exposure amount was 100 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, the base material (A) was peeled off to produce a patterning base material (AI).

[Example 2]
An optical substrate (A-II) was produced in the same manner as in Example 1 except that the laminate (A-2) was used instead of the laminate (A-1).

[Example 3]
A patterning mask was placed on the substrate (B) of the laminate (B-1), and contact exposure was performed using a parallel light exposure machine. The illuminance was 5.0 mW / cm ² and the exposure amount was 100 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, the base material (B) was peeled off to prepare a patterning base material (BI).

[Example 4]
An optical substrate (B-II) was produced in the same manner as in Example 3 except that the laminate (B-2) was used instead of the laminate (B-1).

[Example 5]
An optical substrate (B-III) was produced in the same manner as in Example 3 except that the laminate (B-3) was used instead of the laminate (B-1).

[Example 6]
An optical substrate (B-IV) was produced in the same manner as in Example 3 except that the laminate (B-4) was used instead of the laminate (B-1).

[Comparative Example 1]
A patterning mask was placed over the glass substrate of the laminate (C-1), and contact exposure was performed using a parallel light exposure machine. The illuminance was 5.0 mW / cm ² and the exposure amount was 100 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, the substrate (C) was peeled off to prepare a patterning substrate CI.

  In addition, PLA-501F (made by Canon Inc.) was used for the exposure machine.

[Evaluation method]
The obtained patterning substrate and optical substrate (patterning substrate having a concavo-convex structure) were observed with an optical microscope, and it was confirmed whether or not 100 μm square patterning was formed. The evaluation results are summarized in Table 2 below. However, the residue remaining slightly in the pattern was not taken into consideration, and it was determined whether or not a 100 μm square cut pattern could be confirmed with an optical microscope.
○: The pattern can be confirmed with an optical microscope.
X: A pattern cannot be confirmed with an optical microscope.

  In Examples 1 to 6, a 100 μm square pattern was confirmed on the second substrate side, and the exposed portion remained, while the unexposed portion adhered to the peeled first substrate side. However, in Comparative Example 1, the photosensitive resin material adhered to the quartz on the second substrate side in both the unexposed area and the exposed area.

  Although the concavo-convex structure has been described using the dot pattern, the concavo-convex structure is not limited to this. Examples of the other concavo-convex structure include a line and space. In the case of line and space, the width of the line and space is preferably 3 μm or less, more preferably 1 μm or less, further preferably 700 nm or less, preferably 50 nm or more, more preferably 100 nm or more. More preferably, it is 200 nm or more. The height of the line and space is preferably 3 μm or less, more preferably 1 μm or less, still more preferably 700 nm or less, preferably 50 nm or more, more preferably 100 nm or more, and further preferably 200 nm or more. Arbitrary structures can be selected for the convex and concave shapes in the line add space, and examples thereof include a rectangular shape, a triangular shape, a hemispherical shape, and a dome shape.

  In addition, this invention is not limited to the said embodiment, It can implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effects of the present invention are exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

  Since the resin layer patterned by the surface of the base material can be easily provided for this invention, it can utilize suitably for manufacture of an optical element like LED, for example.

DESCRIPTION OF SYMBOLS 10 Pattern formation laminated body 11 Resin layer 11a Unexposed part 11b Exposed part 12 1st base material 13 2nd base material 21 Patterning mask 24 Base material with pattern 25 Base material with pattern

Claims (12)

A resin layer composed of a photosensitive resin material; a first base material bonded to one main surface of the resin layer; and a second base material bonded to the other main surface of the resin layer. And
At least one of the first base material and the second base material has a concavo-convex structure formed of a resin containing a fluorine compound on at least a part of the surface in contact with the resin layer,
When the resin layer is exposed with a desired pattern to form an unexposed part and an exposed part,
In the unexposed portion, the adhesion with the first substrate is greater than the adhesion with the second substrate, and
In the said exposure part of the said resin layer, adhesiveness with a said 1st base material becomes smaller than adhesiveness with a said 2nd base material. The laminated body for pattern formation characterized by the above-mentioned. The relief structure, periodic pattern forming laminate according to claim 1, wherein the sequence is. The photosensitive resin material and patterning laminate according to claim 1 or claim 2, characterized in that different materials are present in at least a portion of the recess of the uneven structure. The pattern formation according to any one of claims 1 to 3 , wherein at least one of the first substrate and the second substrate is made of an inorganic material. Laminated body. 5. The pattern forming laminate according to claim 4 , wherein the inorganic material is a metal material including a metal, a metal oxide, a metal nitride, or a semiconductor material. The metal oxide is at least one selected from the group consisting of a transparent conductor, silicon oxide, aluminum oxide, titanium oxide, niobium oxide, zirconium oxide, barium titanate and strontium titanate. 5. The laminate for pattern formation according to 5 . 7. The laminate for pattern formation according to claim 6, wherein the transparent conductor is at least one selected from the group consisting of ITO, IZO, ATO, AZO, GZO, TTO, NTO, tin oxide and zinc oxide. body. 6. The laminated body for pattern formation according to claim 5 , wherein the semiconductor material is Si, SiC, Ge, or a III-V group compound. 6. The pattern forming laminate according to claim 5 , wherein the metal is at least one selected from the group consisting of Al, Mo, Au, Ag, Cu, and Ti. The exposure process which exposes the said resin layer through the mask which has a desired pattern with respect to the laminated body for pattern formation in any one of Claim 1 to 9 , and forms the said exposure part and the said unexposed part When,
A peeling step of peeling the laminate for pattern formation into the second base material to which the unexposed part is bonded and the second base material to which the exposed part is bonded;
The manufacturing method of the base material with a pattern characterized by comprising. The process according to claim 1 0 patterned substrate according to, further comprising a heating step of heating the patterned laminate for after the exposure step. Patterned substrate, characterized by being manufactured by the manufacturing method according to claim 1 0 or claim 1 1 patterned substrate according.

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